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WO2018124645A1 - Procédé de fabrication d'électrode, électrode fabriquée par ce procédé, ensemble membrane-électrode comprenant ladite électrode et pile à combustible comprenant ledit ensemble membrane-électrode - Google Patents

Procédé de fabrication d'électrode, électrode fabriquée par ce procédé, ensemble membrane-électrode comprenant ladite électrode et pile à combustible comprenant ledit ensemble membrane-électrode Download PDF

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Publication number
WO2018124645A1
WO2018124645A1 PCT/KR2017/015301 KR2017015301W WO2018124645A1 WO 2018124645 A1 WO2018124645 A1 WO 2018124645A1 KR 2017015301 W KR2017015301 W KR 2017015301W WO 2018124645 A1 WO2018124645 A1 WO 2018124645A1
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Prior art keywords
ionomer
electrode
catalyst
carbon structure
coated
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PCT/KR2017/015301
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English (en)
Korean (ko)
Inventor
김정호
김형수
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Kolon Industries Inc
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Kolon Industries Inc
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Publication date
Priority claimed from KR1020160181590A external-priority patent/KR102189064B1/ko
Priority claimed from KR1020170000025A external-priority patent/KR102175008B1/ko
Application filed by Kolon Industries Inc filed Critical Kolon Industries Inc
Priority to JP2019521674A priority Critical patent/JP6895517B2/ja
Priority to EP17887671.0A priority patent/EP3536664B1/fr
Priority to CN201780066307.3A priority patent/CN109890752A/zh
Priority to US16/343,522 priority patent/US11283093B2/en
Publication of WO2018124645A1 publication Critical patent/WO2018124645A1/fr
Anticipated expiration legal-status Critical
Priority to US17/592,595 priority patent/US11557782B2/en
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/18—Nanoonions; Nanoscrolls; Nanohorns; Nanocones; Nanowalls
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/48—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/48—Macromolecular compounds
    • C04B41/488—Other macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C04B41/4892—Polyamides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/56—Treatment of carbon black ; Purification
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8828—Coating with slurry or ink
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method for manufacturing an electrode, an electrode produced thereby, a membrane-electrode assembly including the electrode, and a fuel cell including the membrane-electrode assembly, wherein the surface of the catalyst is coated with an ionomer at a nano-thickness.
  • the present invention relates to a method for manufacturing an electrode capable of increasing the number of electrodes, an electrode manufactured thereby, a membrane-electrode assembly including the electrode, and a fuel cell including the membrane-electrode assembly.
  • the present invention relates to a method for producing an ionomer-coated carbon structure, and to a carbon structure coated with the ionomer produced thereby, by coating the ionomer on the surface of the carbon structure in nano-thickness, dispersibility of the carbon structure, etc. Increased to facilitate mixing, increase dispersion stability, uniform distribution of ionomers on the surface of the carbon structure, increase the utilization rate of the carbon structure and ionomer to improve various performances, and increase the coupling efficiency of the carbon structure and ionomer
  • the present invention relates to a method for producing an ionomer-coated carbon structure, and to an ionomer-coated carbon structure prepared thereby.
  • a fuel cell is a battery having a power generation system that directly converts chemical reaction energy such as oxidation / reduction reaction of hydrogen and oxygen contained in hydrocarbon-based fuel materials such as methanol, ethanol and natural gas into electrical energy.
  • chemical reaction energy such as oxidation / reduction reaction of hydrogen and oxygen contained in hydrocarbon-based fuel materials such as methanol, ethanol and natural gas
  • hydrocarbon-based fuel materials such as methanol, ethanol and natural gas
  • This fuel cell has a merit that it can produce a wide range of output by stacking by stacking unit cells, and has attracted attention as a small and portable portable power source because it shows an energy density of 4 to 10 times compared to a small lithium battery. have.
  • a stack that substantially generates electricity in a fuel cell is made up of several to dozens of unit cells consisting of a membrane-electrode assembly (MEA) and a separator (also called a bipolar plate).
  • MEA membrane-electrode assembly
  • separator also called a bipolar plate
  • the membrane-electrode assembly has a structure in which an anode (Anode, or fuel electrode) and a cathode (Cathode, or air electrode) are formed on both sides of an electrolyte membrane.
  • Fuel cells may be classified into alkali electrolyte fuel cells and polymer electrolyte fuel cells (PEMFCs) according to the state and type of electrolyte.
  • PEMFCs polymer electrolyte fuel cells
  • polymer electrolyte fuel cells may have a low operating temperature of less than 100 ° C.
  • polymer electrolyte fuel cells include hydrogen exchange gas fuel cells (Proton Exchange Membrane Fuel Cell, PEMFC), and direct methanol fuel cell (DMFC) using liquid methanol as fuel. Etc. can be mentioned.
  • the electrode of the fuel cell is composed of a catalyst and an ionomer, the bonding and dispersity therebetween will greatly affect the performance and durability of the fuel cell.
  • An object of the present invention is to coat the ionomer nano-thickness on the surface of the catalyst, to increase the dispersibility of the catalyst, etc. to facilitate mixing, to evenly distribute the ionomer on the catalyst surface, thereby increasing the utilization rate of the catalyst and ionomer It is to provide a method for producing an electrode that can improve various performances, increase the coupling efficiency of the catalyst and the ionomer and increase durability.
  • Another object of the present invention is to provide an electrode produced by the method for producing the electrode.
  • Still another object of the present invention is to provide a membrane-electrode assembly including the electrode.
  • Another object of the present invention is to coat the ionomer on the surface of the carbon structure to a nano-thickness, thereby increasing the dispersibility of the carbon structure and the like to facilitate mixing, increase the dispersion stability, evenly distributed ionomer on the surface of the carbon structure It is to provide a method for producing an ionomer-coated carbon structure that can increase the utilization of the carbon structure and the ionomer to improve various performances, increase the coupling efficiency of the carbon structure and the ionomer to increase the durability.
  • Still another object of the present invention is to provide an ionomer-coated carbon structure prepared by the method for producing an ionomer-coated carbon structure.
  • preparing a composition for forming an electrode comprising a catalyst and an ionomer by applying a low-frequency acoustic energy (low-frequency acoustic energy) to the composition for forming the electrode by resonant mixing (resonant vibratory mixing) It provides a method for producing an electrode comprising coating the ionomer on the surface of the catalyst, and preparing an electrode by coating the composition for forming the electrode.
  • a low-frequency acoustic energy low-frequency acoustic energy
  • resonant mixing resonant vibratory mixing
  • the low frequency acoustic energy may have a frequency of 10 to 100 Hz.
  • the resonance mixing may be performed by applying an acceleration of 10 to 100 G to the composition for forming an electrode including the catalyst and the ionomer.
  • the resonance mixing may be performed for 30 seconds to 30 minutes.
  • the electrode forming composition may further include a solvent.
  • the present invention comprises a catalyst and ionomer, the ionomer provides an electrode that is coated with a thickness of 5 nm or less on the surface of the catalyst.
  • the ionomer may be coated on the surface of the catalyst by resonant vibratory mixing by applying low-frequency acoustic energy to the composition for forming an electrode including the catalyst and the ionomer.
  • the ionomer coated with a thickness of 5 nm or less on the surface of the catalyst may be 55 wt% to 95 wt% with respect to the total weight of the ionomer.
  • the ionomer that is not coated on the surface of the catalyst and aggregated may be 0 wt% to 45 wt% with respect to the total weight of the ionomer.
  • the catalyst may include catalyst metal particles alone or catalyst metal particles supported on a carrier.
  • a weight ratio (I / C ratio) of the ionomer to the carrier represented by Equation 1 may be 0.75 to 1.6.
  • an anode electrode and a cathode electrode which are located opposite to each other, and an ion exchange membrane positioned between the anode electrode and the cathode electrode, the anode electrode, the cathode electrode and both Any one selected from the group consisting of provides a membrane-electrode assembly comprising the electrode.
  • a fuel cell comprising the membrane-electrode assembly.
  • preparing a mixture comprising a carbon structure and an ionomer by applying low-frequency acoustic energy to the mixture (resonant vibratory mixing) It provides a method for producing an ionomer-coated carbon structure comprising the step of coating the ionomer on the surface of the carbon structure.
  • the carbon structure may include carbon nanotubes, carbon nanowires, graphene, graphene oxide, carbon black, and nanostructured carbon. It may be any one selected from the group consisting of porous carbon and mixtures thereof.
  • the low frequency acoustic energy may have a frequency of 10 to 100 Hz.
  • the resonance mixing may be performed by applying an acceleration of 10 to 100 G to the vessel containing the mixture of the carbon structure and the ionomer under the frequency.
  • the resonance mixing may be performed for 30 seconds to 30 minutes.
  • the mixture may further comprise a solvent.
  • a carbon structure (carbon structure) and ionomer wherein the ionomer is coated on the surface of the carbon structure to a thickness of 5 nm or less to provide an ionomer-coated carbon structure do.
  • the carbon structure is in the group consisting of carbon nano tube (carbon nano tube), carbon nano wire (carbon nano wire), graphene (graphene), graphene oxide (graphene oxide), carbon black (carbon black) and mixtures thereof Can be selected.
  • the ionomer may be coated on the surface of the carbon structure by resonant vibratory mixing by applying low-frequency acoustic energy to the carbon structure and the mixture including the ionomer.
  • An ionomer coated with a thickness of 5 nm or less on the surface of the carbon structure may be 60 wt% to 100 wt% with respect to the total weight of the ionomer.
  • the ionomer that is not coated on the surface of the carbon structure and aggregated may be 0 wt% to 40 wt% based on the total weight of the ionomer.
  • a weight ratio (I / C ratio) of the ionomer to the carbon structure represented by Equation 2 may be 0.75 to 1.6.
  • the dispersibility of the catalyst and the like is increased to facilitate mixing, and the ionomer is uniformly distributed on the catalyst surface, thereby increasing the utilization rate of the catalyst and the ionomer to improve the performance
  • the durability can be increased by increasing the coupling efficiency of the catalyst and the ionomer.
  • the present invention by coating the ionomer nano-thickness on the surface of the carbon structure, to increase the dispersibility of the carbon structure to facilitate mixing, to increase the dispersion stability, to uniformly distribute the ionomer on the surface of the carbon structure,
  • the utilization rate of the carbon structure and the ionomer may be increased to improve various performances, and the coupling efficiency of the carbon structure and the ionomer may be increased to increase durability.
  • FIG. 1 is a schematic diagram showing a process in which an ionomer is coated on a catalyst surface.
  • FIG. 2 is a schematic cross-sectional view of a membrane-electrode assembly according to an embodiment of the present invention.
  • FIG. 3 is a schematic diagram showing the overall configuration of a fuel cell according to an embodiment of the present invention.
  • Figure 4 is a schematic diagram showing a process in which the ionomer is coated on the surface of the carbon structure.
  • TEM 5 and 6 are transmission electron microscope (TEM) photographs of the electrodes prepared in Example 1-1 and Comparative Example 1-1 of the present invention, respectively.
  • Example 7 is a graph showing the results of performance evaluation of the membrane-electrode assembly prepared in Example 1-1 and Comparative Example 1-1 of the present invention.
  • Example 8 is a transmission electron microscope (TEM) photograph of the ionomer-coated carbon structure prepared in Example 2-1 of the present invention.
  • TEM 9 is a transmission electron microscope (TEM) photograph of the carbon structure in which the ionomer prepared in Comparative Example 2-1 of the present invention is mixed.
  • a method of manufacturing an electrode includes preparing a composition for forming an electrode including a catalyst and an ionomer, and applying a low-frequency acoustic energy to the composition for forming the electrode to thereby resonant mixture. vibratory mixing) to coat the ionomer on the surface of the catalyst, and to prepare the electrode by coating the composition for forming an electrode.
  • composition for electrode formation containing a catalyst and an ionomer is manufactured.
  • the catalyst may be any of those that can be used as a catalyst for hydrogen oxidation and oxygen reduction, and preferably a platinum-based metal is used.
  • the platinum-based metal is platinum (Pt), palladium (Pd), ruthenium (Ru), iridium (Ir), osmium (Os), platinum-M alloys (the M is palladium (Pd), ruthenium (Ru), iridium ( Ir), osmium (Os), gallium (Ga), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper ( Cu, silver (Ag), gold (Au), zinc (Zn), tin (Sn), molybdenum (Mo), tungsten (W), lanthanum (La) and rhodium (Rh) It may include one selected from the group consisting of) and a combination thereof, and more preferably, a combination of two or more metals selected from the platinum-based catalyst metal group may be used, but is not limited thereto. Platinum-based catalyst metals usable in the art can be used
  • the catalyst may be a metal itself (black), or may be used by supporting the catalyst metal on a carrier.
  • the carrier may be selected from carbon-based carriers, porous inorganic oxides such as zirconia, alumina, titania, silica, ceria, zeolite, and the like.
  • the carbon-based carrier is a super P, carbon fiber, carbon sheet, carbon black, Ketjen Black, acetylene black, carbon nanotube (carbon nano tube, CNT), carbon sphere (carbon sphere), carbon ribbon (carbon ribbon), fullerene (fullerene), activated carbon and one or more combinations thereof, but is not limited thereto.
  • Carriers usable in can be used without limitation.
  • the catalytic metal particles may be located on the surface of the carrier, or may penetrate into the carrier while filling the internal pores of the carrier.
  • the noble metal supported on the carrier When using the noble metal supported on the carrier as a catalyst, a commercially available commercially available one may be used, or may be prepared by using a noble metal supported on the carrier.
  • the process of supporting the noble metal on the carrier is well known in the art, and thus the detailed description thereof will be easily understood by those skilled in the art.
  • the catalyst metal particles may be contained in an amount of 20% to 80% by weight based on the total weight of the catalyst, and when contained in less than 20% by weight, there may be a problem of deterioration of activity. Aggregation of the catalyst metal particles may reduce the active area, which may in turn lower the catalytic activity.
  • the catalyst may be contained in an amount of 50% by weight to 80% by weight with respect to the total weight of the electrode, when less than 50% by weight may have a problem of deterioration of activity due to the lack of a catalyst, when it exceeds 80% by weight
  • the lack of ionomers can be detrimental to ion conduction.
  • the ionomer may be a cation conductor having a cation exchange group such as proton or an anion conductor having an anion exchange group such as hydroxy ion, carbonate or bicarbonate.
  • the cation exchange group may be any one selected from the group consisting of a sulfonic acid group, a carboxyl group, a boronic acid group, a phosphoric acid group, an imide group, a sulfonimide group, a sulfonamide group, and a combination thereof, and in general, may be a sulfonic acid group or a carboxyl group. have.
  • the cation conductor includes the cation exchange group, the fluorine-based polymer containing fluorine in the main chain; Benzimidazole, polyamide, polyamideimide, polyimide, polyacetal, polyethylene, polypropylene, acrylic resin, polyester, polysulfone, polyether, polyetherimide, polyester, polyethersulfone, polyetherimide, poly Hydrocarbon-based polymers such as carbonate, polystyrene, polyphenylene sulfide, polyether ether ketone, polyether ketone, polyaryl ether sulfone, polyphosphazene or polyphenylquinoxaline; Partially fluorinated polymers such as polystyrene-graft-ethylenetetrafluoroethylene copolymer or polystyrene-graft-polytetrafluoroethylene copolymer; Sulfone imides and the like.
  • the polymers may include a cation exchange group selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphonic acid groups, and derivatives thereof in the side chain thereof.
  • a cation exchange group selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphonic acid groups, and derivatives thereof in the side chain thereof.
  • Specific examples thereof include poly (perfluorosulfonic acid), poly (perfluorocarboxylic acid), copolymers of tetrafluoroethylene and fluorovinyl ether containing sulfonic acid groups, defluorinated sulfide polyether ketones or mixtures thereof.
  • Fluorine-based polymer comprising; Sulfonated polyimide (S-PI), sulfonated polyarylethersulfone (S-PAES), sulfonated polyetheretherketone (SPEEK), sulfonated polybenzimine Sulfonated polybenzimidazole (SPBI), sulfonated polysulfone (S-PSU), sulfonated polystyrene (S-PS), sulfonated polyphosphazene, sulfonated poly Sulfonated polyquinoxaline, sulfonated polyketone, sulfonated polyphenylene oxide, sulfonated polyether sulfone, sulfonated polyether ketone polyether ketone, sulfonated polyphenylene sulfone, sulfonated polyphenylene sulfide, sulfonated polyphenylene sulfide sulfone
  • the cation conductor may also replace H with Na, K, Li, Cs or tetrabutylammonium in the cation exchange group at the side chain end.
  • H when H is replaced with Na, NaOH is substituted during the preparation of the catalyst composition, and when tetrabutylammonium is substituted, tetrabutylammonium hydroxide is used, and K, Li, or Cs is also appropriate.
  • Substitutions may be used. Since the substitution method is well known in the art, detailed description thereof will be omitted.
  • the cationic conductor can be used in the form of a single substance or a mixture, and can also be optionally used with a nonconductive compound for the purpose of further improving adhesion to the ion exchange membrane. It is preferable to adjust the usage-amount so that it may be suitable for a purpose of use.
  • non-conductive compound examples include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and ethylene / tetrafluoro Ethylene / tetrafluoroethylene (ETFE), ethylene chlorotrifluoro-ethylene copolymer (ECTFE), polyvinylidene fluoride, copolymer of polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP), dode
  • PTFE polytetrafluoroethylene
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • PFA tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer
  • ETFE ethylene / tetrafluoro Ethylene / te
  • the anion conductors are polymers capable of transporting anions such as hydroxy ions, carbonates or bicarbonates, and the anion conductors are commercially available in the form of hydroxides or halides (generally chloride), the anion conductors being industrially purified (water purification), metal separation or catalytic processes.
  • a polymer doped with metal hydroxide may be generally used. Specifically, poly (ethersulphone) doped with metal hydroxide, polystyrene, vinyl polymer, poly (vinyl chloride), poly (vinylidene fluoride) , Poly (tetrafluoroethylene), poly (benzimidazole), poly (ethylene glycol) and the like can be used.
  • ionomer examples include nafion, aquibion and the like.
  • the ionomer may be included in an amount of 20 wt% to 50 wt% with respect to the total weight of the electrode. If the content of the ionomer is less than 20% by weight, the generated ions may not be easily transferred. If the amount of the ionomer is more than 50% by weight, the active area may be difficult to supply and react with hydrogen or oxygen (air) due to insufficient porosity. This can be reduced.
  • the electrode forming composition may be prepared by specifically adding the catalyst to the ionomer or by adding the ionomer to the catalyst, and after the addition, the electrode forming composition does not need to be mixed, but the resonance mixing is performed. It is also possible to mix by a general method before. In this case, the general mixing method may be any one or more of the dispersion method selected from ultrasonic dispersion, stirring, three roll mill, ball mill, planetary stirring, high pressure dispersion, and mixing thereof.
  • the electrode forming composition may further include a solvent together with the catalyst and the ionomer.
  • the electrode forming composition may add the catalyst to the solvent to prepare a catalyst solution, and then add the ionomer to the catalyst solution. It may be prepared by adding, the ionomer may be added to the solvent to prepare an ionomer solution, and then the catalyst may be added to the ionomer solution, or the catalyst solution and the ionomer solution may be mixed.
  • the solvent may be a solvent selected from the group consisting of water, a hydrophilic solvent, an organic solvent and one or more mixtures thereof.
  • the hydrophilic solvent is one selected from the group consisting of alcohols, ketones, aldehydes, carbonates, carboxylates, carboxylic acids, ethers, and amides containing, as main chain, linear, branched, saturated or unsaturated hydrocarbons having 1 to 12 carbon atoms. It may have a functional group or more, they may include an alicyclic or aromatic cyclo compound as at least part of the main chain.
  • alcohols include methanol, ethanol, isopropyl alcohol, ethoxy ethanol, n-propyl alcohol, butyl alcohol, 1,2-propanediol, 1-pentanol, 1.5-pentanediol, 1.9-nonanediol, and the like;
  • Ketones include heptanone, octanon and the like;
  • Aldehydes include benzaldehyde, tolualdehyde and the like; Examples of the ester include methylpentanoate, ethyl-2-hydroxypropanoate, and the like;
  • Carboxylic acids include pentanoic acid, heptanoic acid and the like;
  • Ethers include methoxybenzene, dimethoxypropane and the like;
  • Amides include propanamide, butylamide, dimethylacetamide, and the like.
  • the organic solvent may be selected from N-methylpyrrolidone, dimethyl sulfoxide, tetrahydrofuran and mixtures thereof.
  • the solvent may be contained in an amount of 80 to 95% by weight based on the total weight of the composition for forming the electrode, if less than 80% by weight of the solid content is too high may cause dispersion problems due to cracks and high viscosity during electrode coating, If it exceeds 95% by weight, it may be detrimental to electrode activity.
  • the ion forming composition is resonantly mixed to coat the ionomer on the surface of the catalyst.
  • the resonance mixing is a mixing process in which mixing resonates, and the resonance of the mixing may occur as a result of a combination of vibration and acceleration of the mixing components.
  • the resonance mixing generates a large number of powerful mixing regions having a diameter of about 50 ⁇ m, thereby eliminating dead-zones, thereby enabling uniform mixing as a whole.
  • the resonant mixing can minimize the contamination without the need for stirring, such as an impeller, can reduce the loss (Loss), the available viscosity range is 1 cP to more than 1 million cP, it can also adjust the vacuum or temperature .
  • Resodyn ® 0 people's sound mixer Resonant Acoustic Mixer, RAM
  • the inventors of the present invention have found that by using the resonance mixing, the ionomer can be coated on the surface of the catalyst with a nano-thickness of 5 nm or less and completed the present invention.
  • FIG. 1 is a schematic diagram showing a process in which the ionomer is coated on the catalyst surface.
  • the surface of the catalytic metal particles 2 supported on the carrier 1 by the resonance mixing is coated with the ionomer 3 to a nano thickness. That is, the ionomer 3 having a softer shape may be coated onto the surface of the catalytic metal particles 2 having a harder structure by using the resonance mixing.
  • the resonance mixing may be performed by applying low frequency acoustic energy.
  • the low frequency acoustic energy is a straight or spherical energy propagation through a tangible medium in the frequency region of 10 to 20000 Hz, in the present invention, in order to nano-thickly coat the ionomer on the surface of the catalyst, a frequency of 10 to 100 Hz, specifically Low frequency acoustic energy having a frequency of 50 to 70 Hz is used.
  • the resonance mixing may be performed by applying an acceleration of 10 to 100 G, specifically 40 to 100 G, to the composition for forming an electrode including the catalyst and ionomer under the frequency (where G means gravity acceleration, For example, 10 G means 10 times the acceleration of gravity.
  • the coating is not made, the performance may be degraded, if it exceeds 100 G, ionomers agglomerate or change the mixing conditions and performance reduction due to phase separation and heat generation, There may be problems such as flooding.
  • the method for applying the low frequency acoustic energy and the acceleration in the frequency domain to the composition for forming an electrode is not particularly limited in the present invention, and any method known in the art can be used.
  • the acoustic energy is supplied by periodic linear displacement of a container filling the mixture of catalyst and ionomer, using a plurality of mechanical or electron transducer arrangements for this purpose. More specifically, it includes oscillator drives that transfer vibration and acceleration to the vessel and variable elastic members such as springs.
  • the resonance acoustic mixer see US Patent Registration No. 7188993 and US Patent Publication No. 2010-0294113.
  • the resonance mixing may be performed for 30 seconds to 30 minutes, and specifically for a short time for 1 minute to 10 minutes. If the resonance mixing time is less than 30 seconds, less mixing or coating properties may not be confirmed, and if it exceeds 30 minutes, the sample or composition may be changed.
  • the resonance mixing may also mix a wide range of materials such as solid-solid, solid-liquid, liquid-liquid, liquid-gas, and the like.
  • the composition for forming an electrode does not include a solvent
  • Solid-solid mixing comprising only the ionomer is possible
  • solid-liquid or liquid-liquid mixing is also possible wherein the catalyst, the ionomer, and both comprise a solvent.
  • the electrode is prepared by coating the composition for forming an electrode.
  • the preparing of the electrode is not particularly limited in the present invention, but the method may further include preparing an electrode by coating the composition for forming an electrode on a release film, and transferring the electrode to an ion exchange membrane. .
  • the composition for forming the electrode is coated on the release film
  • the composition for forming an electrode including the catalyst is continuously or intermittently transferred to a coater, and then uniformly coated on a release film with a dry thickness of 10 to 200 ⁇ m. It is desirable to.
  • the slot die is transferred to a coater such as a die, gravure, bar, comma coater, etc. continuously through a pump according to the viscosity of the electrode forming composition.
  • Coating, bar coating, comma coating, screen printing, spray coating, doctor blade coating, brush, etc. are used to uniformly apply the dry thickness of the electrode layer on the decal film to 10 to 200 ⁇ m, more preferably 10 to 100 ⁇ m. And evaporate the solvent through a drying furnace maintained at a constant temperature.
  • the activity of the catalyst may be reduced due to a small catalyst content.
  • the resistance may be increased by increasing the moving distance of ions and electrons. have.
  • the drying process may be to dry at least 12 hours at 25 °C to 90 °C. If the drying temperature is less than 25 °C and the drying time is less than 12 hours may cause a problem that can not form a sufficiently dried electrode, when drying at a temperature above 90 °C may cause cracking of the electrode. .
  • coating and drying the said composition for electrode formation is not limited to the above.
  • the method may further include cutting the dried electrode and the release film to a required size and bonding the electrode to the ion exchange membrane.
  • the ion exchange membrane includes an ion conductor.
  • the ion conductor may be a cation conductor having a cation exchange group such as proton or an anion conductor having an anion exchange group such as hydroxy ion, carbonate or bicarbonate.
  • the cation exchange group may be any one selected from the group consisting of a sulfonic acid group, a carboxyl group, a boronic acid group, a phosphoric acid group, an imide group, a sulfonimide group, a sulfonamide group, and a combination thereof, and in general, may be a sulfonic acid group or a carboxyl group. have.
  • the cation conductor includes the cation exchange group, the fluorine-based polymer containing fluorine in the main chain; Benzimidazole, polyamide, polyamideimide, polyimide, polyacetal, polyethylene, polypropylene, acrylic resin, polyester, polysulfone, polyether, polyetherimide, polyester, polyethersulfone, polyetherimide, poly Hydrocarbon-based polymers such as carbonate, polystyrene, polyphenylene sulfide, polyether ether ketone, polyether ketone, polyaryl ether sulfone, polyphosphazene or polyphenylquinoxaline; Partially fluorinated polymers such as polystyrene-graft-ethylenetetrafluoroethylene copolymer or polystyrene-graft-polytetrafluoroethylene copolymer; Sulfone imides and the like.
  • the polymers may include a cation exchange group selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphonic acid groups, and derivatives thereof in the side chain thereof.
  • a cation exchange group selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphonic acid groups, and derivatives thereof in the side chain thereof.
  • Specific examples thereof include poly (perfluorosulfonic acid), poly (perfluorocarboxylic acid), copolymers of tetrafluoroethylene and fluorovinyl ether containing sulfonic acid groups, defluorinated sulfide polyether ketones or mixtures thereof.
  • Fluorine-based polymer comprising; Sulfonated polyimide (S-PI), sulfonated polyarylethersulfone (S-PAES), sulfonated polyetheretherketone (SPEEK), sulfonated polybenzimine Sulfonated polybenzimidazole (SPBI), sulfonated polysulfone (S-PSU), sulfonated polystyrene (S-PS), sulfonated polyphosphazene, Sulfonated polyquinoxaline, sulfonated polyketone, sulfonated polyphenylene oxide, sulfonated polyether sulfone, sulfonated poly Sulfonated polyether ketone, sulfonated polyphenylene sulfone, sulfonated polyphenylene sulfide, sulfonated polyphenylene sulfide sulfone, sulfon
  • the anion conductors are polymers capable of transporting anions such as hydroxy ions, carbonates or bicarbonates, and the anion conductors are commercially available in the form of hydroxides or halides (generally chloride), the anion conductors being industrially purified (water purification), metal separation or catalytic processes.
  • a polymer doped with metal hydroxide may be generally used. Specifically, poly (ethersulphone) doped with metal hydroxide, polystyrene, vinyl polymer, poly (vinyl chloride), poly (vinylidene fluoride) , Poly (tetrafluoroethylene), poly (benzimidazole), poly (ethylene glycol) and the like can be used.
  • the ion exchange membrane may be in the form of a reinforced membrane in which the ion conductor fills pores such as a fluorine-based porous support such as e-PTFE or a porous nanoweb support prepared by electrospinning or the like.
  • a method of bonding the electrode and the ion exchange membrane may use a transfer method, and the transfer method may be performed by applying a heat press to a metal press alone or a soft press of a rubber material such as a silicon rubber material on a metal press to apply heat and pressure. hot pressing) method.
  • the transfer method may be performed under the conditions of 80 °C to 150 °C and 50 kgf / cm 2 to 200 kgf / cm 2 .
  • hot pressing at a temperature of 80 ° C. and less than 50 kgf / cm 2 transfer of the electrode on a release film may not be performed properly, and when it exceeds 150 ° C., the polymer of the ion exchange membrane may burn and There is a risk of structural deformation, and when hot pressing in a condition exceeding 200 kgf / cm 2 , the effect of pressing the electrode is greater than the transfer of the electrode may be a transfer may not be properly performed.
  • Electrode according to another embodiment of the present invention can be manufactured by the above-described electrode manufacturing method.
  • the electrode includes a catalyst and an ionomer, the ionomer is coated on the surface of the catalyst by resonant mixing by applying low frequency acoustic energy to the electrode forming composition comprising the catalyst and the ionomer, wherein the ionomer coating layer is 5 It may have a nano thickness of less than or equal to nm, specifically, a nano thickness of 0.5 to 4 nm. When the thickness of the ionomer coating layer is 5 nm or less, it is preferable in view of performance improvement of the catalyst.
  • ionomer aggregation layers having various thicknesses may be significantly reduced.
  • ionomer aggregation layers having various thicknesses are formed, but when the ionomer is coated on the surface of the catalyst using the resonance mixing, the catalyst has a thickness of 5 nm or less.
  • the ionomer layer to be coated may be formed almost uniformly over the entire area of the electrode.
  • the ionomer coated with a thickness of 5 nm or less on the surface of the catalyst may be 55 to 95 wt%, and specifically 80 to 90 wt%, based on the total weight of the ionomer.
  • the ionomer coated on the surface of the catalyst with a thickness of 5 nm or less is less than 55% by weight relative to the total weight of the ionomer, problems such as reduced performance due to uncoated parts and stability due to limited connection between catalyst and ionomer conjugates And, if it exceeds 95% by weight, the catalytic activity due to the aggregation of ionomers may be lowered.
  • the ionomer agglomeration layer composed of ionomers aggregated without coating on the catalyst surface may be 0 to 45% by weight, and specifically 10 to 20% by weight, based on the total weight of the ionomer.
  • the ionomer flocculating layer exceeds 45 wt% with respect to the total weight of the ionomer, catalytic activity due to agglomeration of the ionomer and an uncoated catalyst may be reduced.
  • An ionomer coated with a thickness of 5 nm or less on the surface of the catalyst means that the electrode is 5 nm or less when observed with a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM), and is not coated on the catalyst surface.
  • Aggregated ionomer means that when the electrode is observed by TEM or STEM, the thickness is greater than 5 nm, or the aggregated ionomer is observed by TEM, STEM or scanning electron microscope (SEM).
  • the ionomer may include ionomers coated with a thickness of 5 nm or less on the surface of the catalyst and ionomers other than the ionomers that are not coated on the surface of the catalyst and aggregated.
  • the content of the ionomer coated on the surface of the catalyst with a thickness of 5 nm or less or the content of the aggregated ionomer may be a content value measured for the entire electrode, and the TEM or STEM image on any at least five places of the electrode.
  • the content of the ionomer or the aggregated ionomer coated on the surface of the present catalyst having a thickness of 5 nm or less may be measured and then calculated by calculating their average value.
  • the ionomer-coated catalyst is detected by fluorine (F) when analyzed by energy dispersive X-ray spectroscopy (EDS) under TEM or SEM analysis conditions.
  • F fluorine
  • EDS energy dispersive X-ray spectroscopy
  • the ionomer-coated catalyst is sulfur (S) when analyzed by energy dispersive X-ray spectroscopy (EDS) under TEM or SEM analysis conditions. ), The distribution of the ionomer can be confirmed, and the coated and uncoated regions can be confirmed by the distribution of the ionomer.
  • the weight ratio (I / C ratio) of the ionomer to the carrier of the catalyst represented by Equation 1 may be 0.75 to 1.6. This may be an improved I / C ratio by 0.05 to 0.2 compared to the existing electrode.
  • the existing electrode does not include an ionomer coating layer of 5 nm or less, and may be manufactured using a conventional mixing method such as a ball mill.
  • the electrode may exhibit an electrochemical active surface area (ECSA) of 1 to 30% performance improvement, and specifically 5 to 20% performance improvement of the existing electrode.
  • ECSA electrochemical active surface area
  • the electrochemically effective surface area may be measured by measuring cyclo-voltammetry using a rotating disk electrode to obtain a hydrogen oxidation area.
  • the existing electrode does not include an ionomer coating layer of 5 nm or less, and may be manufactured using a conventional mixing method such as a ball mill.
  • the membrane-electrode assembly includes an anode electrode and a cathode electrode which face each other, and the ion exchange membrane positioned between the anode electrode and the cathode electrode.
  • Any one selected from the group consisting of the anode electrode, the cathode electrode, and both may include an electrode according to an embodiment of the present invention. Since the description of the electrode and the manufacturing method of the electrode is the same as described above, repeated description is omitted.
  • the membrane-electrode assembly 100 includes the ion exchange membrane 50 and the electrodes 20 and 20 ′ disposed on both surfaces of the ion exchange membrane 50, respectively.
  • the electrode 20, 20 ′ includes an electrode substrate 40, 40 ′ and a catalyst layer 30, 30 ′ formed on the surface of the electrode substrate 40, 40 ′, and the electrode substrate 40, 40 ′.
  • a microporous layer (not shown) including conductive fine particles such as carbon powder and carbon black to facilitate material diffusion between the electrode substrates 40 and 40 'between the catalyst layers 30 and 30'. It may further include.
  • an oxidation reaction is formed on one surface of the ion exchange membrane 50 to generate hydrogen ions and electrons from fuel delivered through the electrode base 40 to the catalyst layer 30.
  • the resulting electrode 20 is called an anode electrode and is disposed on the other surface of the ion exchange membrane 50 and passes through the hydrogen ions and the electrode base 40 'supplied through the ion exchange membrane 50 to the catalyst layer 30'.
  • the electrode 20 'which causes a reduction reaction to generate water from the oxidant transferred to the cathode is called a cathode electrode.
  • the catalyst layers 30, 30 'of the anode and cathode electrodes 20, 20' comprise an electrode according to one embodiment of the invention comprising the catalyst, ionomer and polyacrylic acid.
  • a porous conductive substrate may be used to smoothly supply hydrogen or oxygen.
  • Typical examples thereof include a carbon film, a carbon cloth, a carbon felt, or a metal cloth (a porous film composed of a metal cloth in a fibrous state or a metal film formed on a surface of a cloth formed of polymer fibers). May be used, but is not limited thereto.
  • fluorine-based resin examples include polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene, polyperfluoroalkyl vinyl ether, polyperfluorosulfonyl fluoride alkoxy vinyl ether, and fluorinated ethylene propylene ( Fluorinated ethylene propylene), polychlorotrifluoroethylene or copolymers thereof can be used.
  • the membrane-electrode assembly 100 may be manufactured according to a conventional method of manufacturing a membrane-electrode assembly except for using the electrode according to the present invention as the anode or cathode electrodes 20 and 20 '.
  • a fuel cell according to another embodiment of the present invention includes the membrane-electrode assembly.
  • FIG. 3 is a schematic diagram showing the overall configuration of the fuel cell.
  • the fuel cell 200 includes a fuel supply unit 210 for supplying a mixed fuel in which fuel and water are mixed, and a reforming unit for reforming the mixed fuel to generate a reformed gas including hydrogen gas ( 220, a stack 230 in which a reformed gas including hydrogen gas supplied from the reformer 220 generates an electrical energy by causing an electrochemical reaction with an oxidant, and an oxidant in the reformer 220 and the stack.
  • a fuel supply unit 210 for supplying a mixed fuel in which fuel and water are mixed
  • a reforming unit for reforming the mixed fuel to generate a reformed gas including hydrogen gas ( 220, a stack 230 in which a reformed gas including hydrogen gas supplied from the reformer 220 generates an electrical energy by causing an electrochemical reaction with an oxidant, and an oxidant in the reformer 220 and the stack.
  • the stack 230 induces an oxidation / reduction reaction of a reforming gas including hydrogen gas supplied from the reformer 220 and an oxidant supplied from the oxidant supply unit 240 to generate a plurality of unit cells for generating electrical energy. Equipped.
  • Each unit cell means a cell of a unit for generating electricity, wherein the membrane-electrode assembly for oxidizing / reducing oxygen in an oxidant and a reforming gas containing hydrogen gas, and a reforming gas and an oxidant including hydrogen gas
  • a separator also referred to as a bipolar plate, hereinafter referred to as a "bipolar plate" for feeding to the membrane-electrode assembly.
  • the separator is disposed on both sides of the membrane-electrode assembly at the center. At this time, the separator plates respectively located at the outermost side of the stack may be specifically referred to as end plates.
  • the end plate of the separator plate, the pipe-shaped first supply pipe 231 for injecting the reformed gas containing hydrogen gas supplied from the reforming unit 220, and the pipe-shaped second for injecting oxygen gas The supply pipe 232 is provided, and the other end plate has a first discharge pipe 233 for discharging the reformed gas containing hydrogen gas remaining unreacted in the plurality of unit cells to the outside and the unit cell described above. Finally, the second discharge pipe 234 for discharging the remaining unreacted oxidant to the outside is provided.
  • the electrode may be applied to various fields such as a secondary battery or a capacitor, in addition to the membrane-electrode assembly for the fuel cell.
  • a method of manufacturing an ionomer-coated carbon structure includes preparing a mixture including the carbon structure and the ionomer, and applying low-frequency acoustic energy to the mixture to resonate the same. Coating the ionomer on the surface of the carbon structure by resonant vibratory mixing.
  • the carbon structure is a structure of various shapes made of carbon, and the kind thereof is not particularly limited in the present invention.
  • the carbon structure may have a size of micro to nano level, and is not limited to a specific size or shape.
  • carbon structure examples include carbon nano tube (CNT), carbon nano wire, carbon nanowire, graphene, graphene oxide, carbon black, nano structure Any one selected from the group consisting of carbon (nanostructured carbon), porous carbon (porous carbon) and mixtures thereof.
  • the amount of the ionomer is preferably determined in consideration of the specific surface area of the carbon structure, and the ionomer is typically 30 to 200 parts by weight, specifically 50 parts by weight, based on 100 parts by weight of the carbon structure. To 150 parts by weight. When the content of the ionomer is less than 30 parts by weight, a portion in which the ionomer is uncoated may exist in the carbon structure, and when the amount of the ionomer exceeds 200 parts by weight, an agglomeration portion between the ionomers may occur due to an excessive amount of the ionomer.
  • the mixture may be prepared by specifically adding the carbon structure to the ionomer or by adding the ionomer to the carbon structure, and there is no need to mix the prepared mixture after the addition, but the general method prior to the resonance mixing It is also possible to mix by.
  • the general mixing method may be any one or more of the dispersion method selected from ultrasonic dispersion, stirring, three roll mill, ball mill, planetary stirring, high pressure dispersion, and mixing thereof.
  • the mixture may further include a solvent together with the carbon structure and the ionomer, in which case the mixture may be added to the solvent to prepare a carbon structure solution and then add the ionomer to the carbon structure solution.
  • the ionomer may be prepared by adding the ionomer to the solvent to prepare an ionomer solution, followed by adding the carbon structure to the ionomer solution, or mixing the carbon structure solution and the ionomer solution.
  • the solvent may be a solvent selected from the group consisting of water, a hydrophilic solvent, an organic solvent and a mixture of one or more thereof, and the description of the hydrophilic solvent and the organic solvent is the same as described above, and thus a repetitive description thereof will be omitted.
  • the solvent may be contained in 80 to 95% by weight based on the total weight of the mixture, if less than 80% by weight of the solid content is too high may have dispersion problems due to cracks and high viscosity when applying the ionomer-coated carbon structure And, in excess of 95% by weight, may be detrimental to the activity of the ionomer-coated carbon structure.
  • the mixture is resonantly mixed to coat the ionomer on the surface of the carbon structure.
  • the resonance mixing is a mixing process in which mixing resonates, and the resonance of the mixing may occur as a result of a combination of vibration and acceleration of the mixing components.
  • the resonance mixing generates a large number of powerful mixing regions having a diameter of about 50 ⁇ m, thereby eliminating dead-zones, thereby enabling uniform mixing as a whole.
  • the resonant mixing can minimize the contamination without the need for stirring, such as an impeller, can reduce the loss (Loss), the available viscosity range is 1 cP to more than 1 million cP, it can also adjust the vacuum or temperature .
  • Resodyn ® 0 people's sound mixer Resonant Acoustic Mixer, RAM
  • the inventors of the present invention have found that by using the resonance mixing, the ionomer can be coated on the surface of the carbon structure with a nano-thickness of 5 nm or less and completed the present invention.
  • FIG. 4 is a schematic diagram showing a process of coating the ionomer on the surface of the carbon structure.
  • the surface of the carbon structure 11 is coated with the ionomer 13 to a nano thickness by the resonance mixing. That is, the ionomer 13 having a softer shape may be coated onto the surface of the carbon structure 11 having a harder structure by using the resonance mixing.
  • the resonance mixing may be performed by applying low frequency acoustic energy.
  • the low frequency acoustic energy is a straight or spherical energy propagation through a tangible medium in the frequency region of 10 to 20000 Hz, in the present invention, in order to coat the ionomer in nano-thickness on the surface of the carbon structure, a frequency of 10 to 100 Hz, Specifically, low frequency acoustic energy having a frequency of 50 to 70 Hz is used.
  • the resonance mixing may be performed by applying an acceleration of 10 to 100 G, specifically 40 to 100 G, to the vessel containing the mixture of the carbon structure and the ionomer under the frequency (where G means gravity acceleration, for example, 10 G means 10 times the acceleration of gravity).
  • the coating may not be made, if more than 100G there may be a problem such as agglomeration of ionomers or a change in mixing conditions due to phase separation and exotherm.
  • the resonance mixing may be performed for 30 seconds to 30 minutes, and specifically for a short time for 1 minute to 10 minutes. If the resonance mixing time is less than 30 seconds, less mixing or coating properties may not be confirmed, and if it exceeds 30 minutes, the sample or composition may be changed.
  • the resonant mixing is also possible to mix a wide range of materials, such as solid-solid, solid-liquid, liquid-liquid, liquid-gas, such that, using the resonant mixing, the mixture does not contain a solvent and the carbon structure and the ionomer
  • Solid-solid mixing comprising only is possible, and solid-liquid or liquid-liquid mixing is also possible in which the carbon structure, the ionomer, and both comprise a solvent.
  • the ionomer-coated carbon structure according to another embodiment of the present invention may be prepared by the method for producing the ionomer-coated carbon structure.
  • the ionomer-coated carbon structure includes a carbon structure and an ionomer, and the ionomer is subjected to resonance mixing by applying low frequency acoustic energy to the mixture including the carbon structure and the ionomer and coated on the surface of the carbon structure.
  • the ionomer coating layer may have a nano-thickness of 5 nm or less, specifically, 0.5 to 4 nm. When the thickness of the ionomer coating layer is 5 nm or less, it is preferable in terms of utilization of the carbon structure.
  • ionomer aggregation layers having various thicknesses may be significantly reduced.
  • the ionomer coated with a thickness of 5 nm or less on the surface of the carbon structure may be 60 wt% to 100 wt% with respect to the total weight of the ionomer, and specifically 85 Weight percent to 95 weight percent. If the ionomer coated with a thickness of 5 nm or less on the surface of the carbon structure is less than 60% by weight relative to the total weight of the ionomer, an uncoated region may occur, and when the amount of the ionomer is greater than 100% by weight, aggregated portions of the ionomer may occur. have.
  • the ionomer agglomeration layer composed of the ionomers not coated on the surface of the carbon structure may be 0 wt% to 40 wt% with respect to the total weight of the ionomer, and specifically 1 wt% to 15 wt%. If the ionomer aggregation layer exceeds 40% by weight relative to the total weight of the ionomer, aggregated regions of the ionomer may occur.
  • the ionomer coated with a thickness of 5 nm or less on the surface of the carbon structure means that the carbon structure coated with the ionomer is 5 nm or less when observed with an electron microscope (TEM) or a scanning transmission electron microscope (STEM).
  • TEM electron microscope
  • STEM scanning transmission electron microscope
  • Agglomerated ionomers that are not coated on the surface of the structure have a thickness greater than 5 nm when the ionomer-coated carbon structures are observed by TEM or STEM, or that agglomerated ionomers are observed by TEM, STEM or Scanning Electron Microscopy (SEM). it means.
  • the ionomer may include an ionomer coated with a thickness of 5 nm or less on the surface of the carbon structure and an ionomer other than the ionomer that is not coated on the surface of the carbon structure and aggregated.
  • the content of the ionomer coated with a thickness of 5 nm or less on the surface of the carbon structure or the content of the aggregated ionomer may be a content value measured for the entire carbon structure coated with the ionomer, and any of the ionomer coated carbon structures It is also possible to calculate the average value of the ionomers coated on the surface of the carbon structures present on the transmission electron microscopy (TEM) photograph for at least five places of the ionized or aggregated ionomers and calculate their average value. have.
  • TEM transmission electron microscopy
  • the ionomer when the ionomer is a fluorine-based ionomer, the ionomer-coated carbon structure is detected by fluorine (F) when analyzed by energy dispersive X-ray spectroscopy (EDS) under TEM or SEM analysis conditions.
  • F fluorine
  • EDS energy dispersive X-ray spectroscopy
  • the ionomer-coated carbon structure is analyzed by sulfur (EMS) analysis by energy dispersive X-ray spectroscope (EDS) under TEM or SEM analysis conditions.
  • EMS sulfur
  • EDS energy dispersive X-ray spectroscope
  • the distribution of the ionomer can be confirmed by the detection of S), and the coated and uncoated regions can be identified by the distribution of the ionomer.
  • the weight ratio (I / C ratio) of the ionomer to the carbon structure represented by Equation 2 may be 0.75 to 1.6. This may be an improved I / C ratio by 0.05 to 0.2 compared to the mixture of the existing carbon structure and the ionomer.
  • the mixture of the existing carbon structure and the ionomer does not include an ionomer coating layer of 5 nm or less, and may be prepared using a conventional mixing method such as a ball mill.
  • the ionomer-coated carbon structure exhibits a dispersion stability of 0.5 days to 15 days, specifically 1 day to 8 days in a range where visual layer separation does not occur when left in a solvent after being dispersed in a solvent with various dispersion apparatuses. Can be. If the dispersion stability is less than 0.5 days, it means that the ionomer layer is not coated.
  • the ionomer-coated carbon structure can be applied to catalyst carriers, electrode materials, etc. in the field of electrochemical devices such as fuel cells, secondary cells or capacitors.
  • the vessel containing the mixture was mounted in a Resodyn ® Resonant Acoustic Mixer (RAM).
  • the composition for forming an electrode was prepared by adding low frequency acoustic energy having a frequency of 60 Hz to the resonance acoustic mixer for 5 minutes with an acceleration of 70 G.
  • the electrode-forming composition was bar-coated on a polyimide release film under conditions of a coating speed of 10 mm / s and a coating thickness of 100 ⁇ m, and then dried at 30 ° C. for 6 hours to prepare electrodes.
  • the membrane was subjected to the same procedure as in Example 1-1 except that the resonance acoustic mixer was mixed for 10 minutes with an acceleration of 70 G while applying low frequency acoustic energy having a frequency of 60 Hz to the resonance acoustic mixer.
  • An electrode assembly was prepared.
  • the membrane was subjected to the same procedure as in Example 1-1 except that the resonance acoustic mixer was mixed for 5 minutes with an acceleration of 80 G while applying low frequency acoustic energy having a frequency of 60 Hz to the resonance acoustic mixer.
  • An electrode assembly was prepared.
  • the vessel containing the mixture was mounted in a Resodyn ® Resonant Acoustic Mixer (RAM).
  • the composition for forming an electrode was prepared by adding low frequency acoustic energy having a frequency of 60 Hz to the resonance acoustic mixer for 5 minutes with an acceleration of 70 G.
  • the electrode-forming composition was bar-coated on a polyimide release film under conditions of a coating speed of 10 mm / s and a coating thickness of 100 ⁇ m, and then dried at 30 ° C. for 6 hours to prepare electrodes.
  • the mixture was dispersed and stirred using a ball mill to prepare a composition for forming an electrode.
  • the step of preparing the membrane-electrode assembly by coating and drying the electrode forming composition on a decal film was performed in the same manner as described in the above embodiment to prepare a membrane-electrode assembly.
  • Example 1-1 in the electrode manufactured by resonance mixing as in Example 1-1, a coating phenomenon of ionomer is clearly observed on the surface of the catalyst, and the coating thickness is 5 nm or less. .
  • the wave pattern of the arrow portion (A) in Figure 5 indicates that the ionomer is coated with 5 nm or less, it can be seen that the coating portion is spread throughout.
  • the stacking phenomenon (B) in which the ionomers represented in Comparative Example 1-1 manufactured by the ball mill is stacked is not observed.
  • the voltage and current output from the electrode were measured for the membrane-electrode assemblies prepared in Examples 1-1 and Comparative Example 1-1, and the output characteristics (discharge performance) of the voltage-current density were compared and evaluated. 7 is shown.
  • the membrane-electrode assembly manufactured in the above example has superior voltage performance according to the current density, compared to the membrane-electrode assembly manufactured in the comparative example. It can be seen that the electrode exhibits a larger electrochemically effective surface area than that of the electrode prepared in the comparative example, that is, the activity of the catalyst is increased.
  • the vessel containing the mixture was mounted in a Resodyn ® Resonant Acoustic Mixer (RAM).
  • An ionomer-coated carbon structure was prepared by mixing the resonance acoustic mixer with low frequency acoustic energy having a frequency of 60 Hz for 5 minutes with an acceleration of 70 G.
  • the ionomer was carried out in the same manner as in Example 2-1 except that the resonance acoustic mixer was mixed for 10 minutes with an acceleration of 70 G while applying low frequency acoustic energy having a frequency of 60 Hz to the resonance acoustic mixer. To prepare a coated carbon structure.
  • the ionomer was carried out in the same manner as in Example 2-1 except that the resonance acoustic mixer was mixed for 5 minutes with an acceleration of 80 G while applying low frequency acoustic energy having a frequency of 60 Hz to the resonance acoustic mixer. To prepare a coated carbon structure.
  • Example 2-1 An ionomer-coated carbon structure was prepared in the same manner as in Example 2-1, except that graphene was used as the carbon structure in Example 2-1.
  • Example 2-1 An ionomer-coated carbon structure was prepared in the same manner as in Example 2-1, except that carbon black was used as the carbon structure in Example 2-1.
  • the vessel containing the mixture was mounted in a Resodyn ® Resonant Acoustic Mixer (RAM).
  • An ionomer-coated carbon structure was prepared by mixing the resonance acoustic mixer with low frequency acoustic energy having a frequency of 60 Hz for 5 minutes with an acceleration of 70 G.
  • the mixture was dispersed and stirred using a ball mill to prepare a carbon structure in which ion conductors were mixed.
  • the ionomer-coated carbon structure prepared by resonant mixing as in Example 2-1 is clearly observed in the ionomer coating on the surface of the carbon structure, the coating thickness is 5 It can be confirmed that it is nm or less.
  • the wave pattern of the arrow portion (A) in Figure 8 indicates that the ionomer is coated with 5 nm or less, it can be seen that the coating portion is spread throughout.
  • the stacking phenomenon (B) in which the ionomers represented in Comparative Example 2-1 manufactured by the ball mill is stacked is not observed.
  • stack 231 first supply pipe
  • second discharge pipe 240 oxidant supply unit
  • the present invention relates to a method for manufacturing an electrode, an electrode produced thereby, a membrane-electrode assembly including the electrode, and a fuel cell including the membrane-electrode assembly, wherein the electrode manufacturing method includes an ionomer on a surface of a catalyst. Is coated with a nano-thickness to increase the dispersibility of the catalyst and the like to facilitate mixing, uniform distribution of ionomers on the surface of the catalyst, increase the utilization rate of the catalyst and ionomer to improve various performances, and improve the performance of the catalyst and ionomer The durability can be increased by increasing the binding efficiency.
  • the present invention also relates to a method for producing an ionomer-coated carbon structure, and to a method for producing an ionomer-coated carbon structure, wherein the method for preparing an ionomer-coated carbon structure is nano-thick to the surface of the carbon structure.
  • durability of the carbon structure and the ionomer may be increased by increasing the coupling efficiency.
  • the ionomer-coated carbon structure can be applied to catalyst carriers, electrode materials, etc. in the field of electrochemical devices such as fuel cells, secondary cells or capacitors.

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Abstract

La présente invention concerne un procédé de fabrication d'une électrode, une électrode fabriquée par ce procédé, un ensemble membrane-électrode comprenant cette électrode, ainsi qu'une pile à combustible comprenant cet ensemble membrane-électrode. Ledit procédé de fabrication d'une électrode comprend les étapes consistant à : préparer une composition de formation d'électrode par mélange d'un catalyseur avec un ionomère; appliquer une énergie acoustique basse fréquence à la composition de formation d'électrode pour effectuer un mélange vibratoire résonant de manière à appliquer l'ionomère sur la surface du catalyseur; et appliquer la composition de formation d'électrode pour fabriquer une électrode. Le procédé de fabrication d'une électrode applique l'ionomère sur la surface du catalyseur avec une épaisseur nanométrique pour augmenter la dispersibilité du catalyseur, etc., ce qui facilite le mélange. De plus, le procédé de fabrication d'une électrode répartit uniformément l'ionomère sur la surface du catalyseur pour augmenter le taux d'utilisation du catalyseur et de l'ionomère, ce qui permet d'améliorer diverses performances et d'augmenter l'efficacité de couplage entre le catalyseur et l'ionomère, de telle sorte que la durabilité est améliorée.
PCT/KR2017/015301 2016-12-28 2017-12-22 Procédé de fabrication d'électrode, électrode fabriquée par ce procédé, ensemble membrane-électrode comprenant ladite électrode et pile à combustible comprenant ledit ensemble membrane-électrode Ceased WO2018124645A1 (fr)

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JP2019521674A JP6895517B2 (ja) 2016-12-28 2017-12-22 電極の製造方法、これによって製造された電極、前記電極を含む膜−電極アセンブリー、そして前記膜−電極アセンブリーを含む燃料電池
EP17887671.0A EP3536664B1 (fr) 2016-12-28 2017-12-22 Procédé de fabrication d'électrode, électrode fabriquée par ce procédé, ensemble membrane-électrode comprenant ladite électrode et pile à combustible comprenant ledit ensemble membrane-électrode
CN201780066307.3A CN109890752A (zh) 2016-12-28 2017-12-22 电极的制备方法，由该法制备的电极，含该电极的膜电极组件及含该膜电极组件的燃料电池
US16/343,522 US11283093B2 (en) 2016-12-28 2017-12-22 Method for manufacturing electrode, electrode manufactured thereby, membrane-electrode assembly comprising same electrode, and fuel cell including same membrane-electrode assembly
US17/592,595 US11557782B2 (en) 2016-12-28 2022-02-04 Method for manufacturing electrode, electrode manufactured thereby, membrane-electrode assembly comprising same electrode, and fuel cell including same membrane-electrode assembly

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KR10-2016-0181590 2016-12-28
KR1020160181590A KR102189064B1 (ko) 2016-12-28 2016-12-28 전극의 제조 방법, 이에 의하여 제조된 전극, 상기 전극을 포함하는 막-전극 어셈블리, 그리고 상기 막-전극 어셈블리를 포함하는 연료 전지
KR10-2017-0000025 2017-01-02
KR1020170000025A KR102175008B1 (ko) 2017-01-02 2017-01-02 이오노머가 코팅된 탄소 구조체의 제조 방법, 그리고 이에 의하여 제조된 이오노머가 코팅된 탄소 구조체

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US17/592,595 Division US11557782B2 (en) 2016-12-28 2022-02-04 Method for manufacturing electrode, electrode manufactured thereby, membrane-electrode assembly comprising same electrode, and fuel cell including same membrane-electrode assembly

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US11283093B2 (en) 2022-03-22
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